Cosmetic preparation containing crosslinkable silicone rubber emulsion and its production method

ABSTRACT

A cosmetic preparation containing a crosslinkable silicone rubber emulsion comprising (A) 100 parts by weight of a straight chain or branched organopolysiloxane containing at least two hydroxyl groups bonded to the silicon atom per molecule prepared by ring-opening polymerization of a cyclic organosiloxane in the presence of an alkoxysilane or its partial hydrolytic condensate or an α,ω-dihydroxy or dialkoxy siloxane oligomer by using a catalyst selected from citric, lactic, and ascorbic acids and an anionic surfactant emulsifier; and (B) 0.5 to 20 parts by weight of a reaction product of an amino group-containing organoxysilane and an acid anhydride.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a 37 C.F.R. § 1.53(b) divisional of, andclaims priority to, U.S. application Ser. No. 13/778,585, filed on Feb.27, 2013, now U.S. Pat. No. 9,237,997. Priority is claimed to JapaneseApplication No. 2012-043952, filed on Feb. 29, 2012. The entire contentsof those priority applications are hereby incorporated by reference.

TECHNICAL FIELD

This invention relates to a cosmetic preparation containing acrosslinkable silicone rubber emulsion which can be produced by a simplemethod, and which exhibits lower skin irritancy. This invention alsoproposes its production method.

BACKGROUND ART

Aqueous emulsion of a silicone rubber resin has been known in the art,and various products are on the market including those intended for thecosmetic preparation. However, almost all such commercially availableproducts for the application of cosmetic preparation are silicone rubberresins emulsified and dispersed in water by using a silicone oil or thelike, and these products can not be regarded as a product in an aqueoussystem. JP-A H10-175816 discloses the system wherein silicone rubberparticles are synthesized, dried, and again emulsified and dispersed,and this process requires the steps of drying and emulsification inaddition to the step of the polymerization. Another known products areaqueous dispersions of the silicone rubber by addition reaction of ahydrogen polysiloxane and a vinyl polysiloxane. These products, however,tend to undergo separation, and because of such separation, almost allof these aqueous dispersions were used in the form of powder afterseparation and they were rarely used in the cosmetic preparation in theform of an aqueous dispersion. In another method, the silicone rubberproduced, for example, by solution polymerization is dissolved again ina silicone oil, and then subjected to mechanical emulsification (JP-AH08-245881). This method is economically disadvantageous.

Silicone emulsions capable of forming a film by crosslinking have alsobeen disclosed in JP-A 2007-51236, and these products are in the marketsince their high strength and softness as well as water repellency werehighly evaluated. These are products prepared by simple emulsionpolymerization using a siloxane for the starting material, and thuseconomically advantageous. These products, however, containedsurfactants and acids unsuitable for cosmetic products.

JP-A H11-71522 discloses a polyorganosiloxane emulsion prepared byemulsion polymerization of a silanol group-endcappedpolydiorganosiloxane in the presence of (B) an unsaturated aliphaticsulfonate and/or sulfonate methyl hydroxide formed in the reactionsystem of a sulfonate salt and an acid and (C) water. Thispolyorganosiloxane emulsion, however, uses sulfuric acid, hydrochloricacid, formic acid, and sulfonic acid in its production. These acids aremostly strong acids under the restriction of Poisonous and DeleteriousSubstances Control Act and other laws, and their use in the applicationof cosmetic preparation is unsuitable. Formic acid which is not a strongacid is also under the restriction of Poisonous and DeleteriousSubstances Control Act as a deleterious substance when used at a highconcentration, and its use in the application of cosmetic preparation isalso unsuitable.

JP-B S44-20116 discloses an emulsion polymerization method of anorganosiloxane and a silanol group-containing disilcarbane in an aqueousmedium in the presence of a sulfonic acid catalyst having surfactantactivity selected from benzene sulfonic acid substituted with analiphatic hydrocarbon group, naphthalene sulfonic acid, aliphatichydrocarbon sulfonic acid, and silylalkylsulfonic acid, which is mosttypically an alkylbenzene sulfonic acid such as dodecylbenzene sulfonicacid. However, these are silicone oils, and they are used in a mannerclearly different from the silicone rubber. As in the case ofliteratures as described above, the acid used is a strong acid which isunsuitable for use in the application of cosmetic preparation.

Such polymerization also inevitably involves use of an anionicsurfactant such as sodium laurylsulfate or sodium laureth sulfate.However, these compounds, are irritant and under the restriction of Lawconcerning Pollutant Release and Transfer Register (hereinafter alsoreferred to as PRTR). Also, these compounds may be toxic to human andenvironment (aquatic life), and accordingly, they are not suitable as amaterial used in cosmetic preparations.

In addition, properties such as high spreadability, lighter texture, andsofter touch are expected for a preparation used in cosmeticapplications.

SUMMARY OF INVENTION Technical Problem

The present invention has been completed in view of the situation asdescribed above, and an object of the present invention is to provide acosmetic preparation containing a crosslinkable silicone rubber emulsionwhich has been prepared by solely using ingredients which are not underthe restriction of Poisonous and Deleterious Substances Control Act andLaw concerning Pollutant Release and Transfer Register and which are nothard on the skin, and which exhibits performance equivalent tocommercial silicone rubber emulsions, and which is in the form usablefor the application of cosmetic preparations. Another object of thepresent invention is to provide its production method.

Solution to Problem

In order to achieve the objects as described above, the inventors of thepresent invention made an intensive investigation and found that, astraight chain or branched organopolysiloxane prepared by ring-openingpolymerization using a cyclic organosiloxane for the main startingmaterial, citric acid, lactic acid, or ascorbic acid for the catalyst,and an anionic surfactant, and in particular, an N-acylamino acid salt,an N-acyltaurinate, an aliphatic soap, or an alkylphosphate salt for theemulsifier is suitable as an organopolysiloxane for use in a cosmeticpreparation; and that a mixture of such organopolysiloxane with thereaction product of an amino group-containing organoxysilane and an acidanhydride is effective as a component of a cosmetic preparation. Thepresent invention has been completed on the bases of such findings.

Accordingly, the present invention provides a cosmetic preparation andits production method as described below.

[1]A cosmetic preparation containing a crosslinkable silicone rubberemulsion comprising

(A) 100 parts by weight of a straight chain or branchedorganopolysiloxane containing at least two hydroxyl groups bonded tosilicon atoms per molecule prepared by ring-opening polymerization of acyclic organosiloxane in the presence of an alkoxysilane or its partialhydrolytic condensate or an α,ω-dihydroxy or dialkoxy siloxane oligomerby using at least one member selected from citric acid, lactic acid, andascorbic acid as a catalyst and using an anionic surfactant as anemulsifier; and

(B) 0.5 to 20 parts by weight of a reaction product of an aminogroup-containing organoxysilane and an acid anhydride.

[2]A cosmetic preparation according to [1] wherein the straight chain orbranched organopolysiloxane of component (A) is represented by thefollowing general formula (1):

wherein R is independently an alkyl group containing 1 to 20 carbonatoms or an aryl group containing 6 to 20 carbon atoms; X isindependently an alkyl group containing 1 to 20 carbon atoms, an arylgroup containing 6 to 20 carbon atoms, an alkoxy group containing 1 to20 carbon atoms, or hydroxyl group; Y is independently X or a grouprepresented by —[O—Si(X)₂]_(c)—X, at least 2 of X and Y being hydroxylgroup; letter a is an integer of 0 to 1,000; letter b is an integer of100 to 10,000; and letter c is an integer of 1 to 1,000; with theproviso that each constitutional repeating unit may be randomly bonded.[3]A cosmetic preparation according to [1] or [2] wherein the aminogroup-containing organoxysilane of component (B) is the one representedby the following general formula (2):A(R)_(g)Si(OR)_(3-g)  (2)wherein R is independently an alkyl group containing 1 to 20 carbonatoms or an aryl group containing 6 to 20 carbon atoms, A is anamino-containing group represented by the formula: —R¹(NHR¹)_(h)NHR²wherein R¹ is independently a divalent hydrocarbon group containing 1 to6 carbon atoms, R² is R or hydrogen atom, and letter h is an integer of0 to 6, and letter g is 0, 1, or 2, and the acid anhydride is adicarboxylic acid anhydride.[4]A cosmetic preparation according to any one of [1] to [3] wherein thecatalyst for obtaining the component (A) is citric acid.[5]A cosmetic preparation according to any one of [1] to [4] wherein theanionic surfactant for obtaining the component (A) is at least onemember selected from N-acylamino acid salt, N-acyltaurinate, aliphaticsoap, and alkylphosphate salt.[6]A cosmetic preparation according to any one of [1] to [5] which isfor low-irritant skin care.[7]A method for producing a cosmetic preparation comprising the steps of

producing a crosslinkable silicone rubber emulsion comprising a straightchain or branched organopolysiloxane (A) containing at least twohydroxyl groups bonded to silicon atoms per molecule prepared byring-opening polymerization of a cyclic organosiloxane preferably at atemperature of 55 to 85° C., more preferably at a temperature of 65 to75° C. in the presence of an alkoxysilane or its partial hydrolyticcondensate or an α,ω-dihydroxy or dialkoxy siloxane oligomer by using atleast one member selected from citric acid, lactic acid, and ascorbicacid as a catalyst and using an anionic surfactant as an emulsifier; and

mixing the silicon rubber emulsion with a reaction product (B) of anamino group-containing organoxysilane and an acid anhydride at a mixingratio of 0.5 to 20 parts by weight of the component (B) in relation to100 parts by weight of the organopolysiloxane (A).

[8]A method for producing a cosmetic preparation according to [7]wherein the straight chain or branched organopolysiloxane of component(A) is represented by the following general formula (1):

wherein R is independently an alkyl group containing 1 to 20 carbonatoms or an aryl group containing 6 to 20 carbon atoms; X isindependently an alkyl group containing 1 to 20 carbon atoms, an arylgroup containing 6 to 20 carbon atoms, an alkoxy group containing 1 to20 carbon atoms, or hydroxyl group; Y is independently X or a grouprepresented by —[O—Si(X)₂]_(c)—X, at least 2 of X and Y being hydroxylgroup; letter a is an integer of 0 to 1,000; letter b is an integer of100 to 10,000; and letter c is an integer of 1 to 1,000; with theproviso that each constitutional repeating unit may be randomly bonded.[9]A method for producing a cosmetic preparation according to [7] or [8]wherein the amino group-containing organoxysilane of component (B) isthe one represented by the following general formula (2):A(R)_(g)Si(OR)_(3-g)  (2)wherein R is independently an alkyl group containing 1 to 20 carbonatoms or an aryl group containing 6 to 20 carbon atoms, A is anamino-containing group represented by the formula: —R¹(NHR)_(h)NHR²wherein R¹ is independently a divalent hydrocarbon group containing 1 to6 carbon atoms, R² is R or hydrogen atom, and letter h is an integer of0 to 6, and letter g is 0, 1, or 2, and the acid anhydride is adicarboxylic acid anhydride.[10]A method for producing a cosmetic preparation according to any oneof [7] to [9] wherein the catalyst for obtaining the component (A) iscitric acid.[11]A method for producing a cosmetic preparation according to any oneof [7] to [10] wherein the catalyst for obtaining the component (A) isused in an amount of 0.01 to 10 parts by weight in relation to 100 partsby weight of the cyclic organosiloxane.[12]A method for producing a cosmetic preparation according to any oneof [7] to [11] wherein the anionic surfactant for obtaining thecomponent (A) is at least one member selected from N-acylamino acidsalt, N-acyltaurinate, aliphatic soap, and alkylphosphate salt, and theanionic surfactant is used in an amount of 0.1 to 20 parts by weight inrelation to 100 parts by weight of the cyclic organosiloxane.

Advantageous Effects of Invention

The crosslinkable silicone rubber emulsion used in the cosmeticpreparation of the present invention exhibits performance comparable tothe conventional silicone rubber emulsions while it is prepared fromingredients which are not under the restriction of Poisonous andDeleterious Substances Control Act and Law concerning Pollutant Releaseand Transfer Register and which are not hard on the skin. Due to the useof such silicone rubber emulsion, the cosmetic preparation has reducedenvironmental burden, less irritancy to the skin, higher waterresistance, and higher comfortability in use.

DESCRIPTION OF EMBODIMENTS

The cosmetic preparation of the present invention contains a siliconerubber emulsion comprising

(A) 100 parts by weight of a straight chain or branchedorganopolysiloxane containing at least two hydroxyl groups bonded to thesilicon atom per molecule prepared by ring-opening polymerization of acyclic organosiloxane in the presence of an alkoxysilane or its partialhydrolytic condensate or an α,ω-dihydroxy or dialkoxy siloxane oligomerby using at least one member selected from citric acid, lactic acid, andascorbic acid as a catalyst and using an anionic surfactant as anemulsifier; and

(B) 0.5 to 20 parts by weight of a reaction product of an aminogroup-containing organoxysilane and an acid anhydride.

The organopolysiloxane of the component (A) contains at least 2 hydroxygroups bonded to the silicon atom per molecule, and thisorganopolysiloxane is preferably a straight chain or branchedorganopolysiloxane represented by the following general formula (1):

wherein R is independently an alkyl group containing 1 to 20 carbonatoms or an aryl group containing 6 to 20 carbon atoms; X isindependently an alkyl group containing 1 to 20 carbon atoms, an arylgroup containing 6 to 20 carbon atoms, an alkoxy group containing 1 to20 carbon atoms, or hydroxyl group; Y is independently X or a grouprepresented by —[O—Si(X)₂]_(c)—X, at least 2 of X and Y being hydroxylgroup; letter a is an integer of 0 to 1,000; letter b is an integer of100 to 10,000; and letter c is an integer of 1 to 1,000; with theproviso that each constitutional repeating unit may be randomly bonded.

In the formula, R is independently an alkyl group containing 1 to 20carbon atoms or an aryl group containing 6 to 20 carbon atoms. Examplesof the R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl,cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, and naphthylgroups, and the preferred is methyl group.

X is independently an alkyl group containing 1 to 20 carbon atoms, anaryl group containing 6 to 20 carbon atoms, an alkoxy group containing 1to 20 carbon atoms, or hydroxyl group, and examples include hydroxylgroup, and groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl,cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, naphthyl, methoxy,ethoxy, propoxy, butoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, andtetradecyloxy groups.

Y is independently X or a group represented by —[O—Si(X)₂]_(c)—X.

Letter a is an integer of 0 to 1,000, and preferably 0 to 200 since theinteger in excess of 1,000 will result in the insufficient strength ofthe resulting film. Letter b is an integer of 100 to 10,000, andpreferably 1,000 to 5,000 since the integer of less than 100 will resultin the poor softness of the resulting film while the integer in excessof 10,000 will invite loss of film tear strength. Letter c is an integerof 1 to 1,000.

In view of the crosslinkability, at least 2, and preferably 2 to 4hydroxyl groups are present per molecule preferably at opposite ends.

Exemplary organopolysiloxanes include:

wherein a, b, and c are as defined above.

The straight chain or branched organopolysiloxane is obtained by using acyclic organosiloxane for its main ingredient, and also using analkoxysilane or its partial hydrolytic condensate or α,ω-dihydroxy ordialkoxy siloxane oligomer. The most preferred is alkoxysilane.

In this case, exemplary cyclic organosiloxanes include:

-   hexamethylcyclotrisiloxane (D3),-   octamethylcyclotetrasiloxane (D4),-   decamethylcyclopentasiloxane (D5),-   dodecamethylcyclohexasiloxane (D6),-   1,1-diethylhexamethylcyclotetrasiloxane,-   phenylheptamethylcyclotetrasiloxane,-   1,1-diphenylhexamethylcyclotetrasiloxane,-   1,3,5,7-tetravinyltetramethylcyclotetrasiloxane,-   1,3,5,7-tetramethylcyclotetrasiloxane,-   1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane,-   tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane,-   1,3,5,7-tetra(3-methacryloxypropyl)tetramethylcyclotetrasiloxane,-   1,3,5,7-tetra(3-acryloxypropyl)tetramethylcyclotetrasiloxane,-   1,3,5,7-tetra(3-carboxypropyl)tetramethylcyclotetrasiloxane,-   1,3,5,7-tetra(3-vinyloxypropyl)tetramethylcyclotetrasiloxane,-   1,3,5,7-tetra(p-vinylphenyl)tetramethylcyclotetrasiloxane,-   1,3,5,7-tetra[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane,    and-   1,3,5,7-tetra(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane,-   1,3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane,    namely, D3 to D20 representing the number of cyclic dimethylsiloxane    unit (D: molecular formula, SiO(CH₃)₂).

The preferred is a cyclic siloxane represented by [SiO(CH₃)₂]_(n)wherein n is an integer of 3 to 10.

The more preferred are octamethylcyclotetrasiloxane, anddecamethylcyclopentasiloxane.

Exemplary alkoxysilanes include methyltrimethoxysilane,methyltriethoxysilane, methyltripropoxysilane, methyltributhoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane,propyltriethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane,hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane,dodecyltrimethoxysilane, tetradecyltrimethoxysilane,octadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,3,3,3-trifluoropropyltrimethoxysilane,3,3,3-trifluoropropyltriethoxysilane, tetramethoxy silane,tetraethoxysilane, tetrapropoxysilane, and tetrabuthoxysilane.

Among these, the preferred are methyltrimethoxysilane,methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane,3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.

The alkoxysilane or its partial hydrolytic condensate or anα,ω-dihydroxy or dialkoxy siloxane oligomer is preferably used in anamount of 0.01 to 5 parts by weight, more preferably 0.01 to 2 parts byweight, and still more preferably 0.01 to 1 part by weight in relationto 100 parts by weight of the cyclic organosiloxane.

In the present invention, the organopolysiloxane of the formula (1) isobtained from the starting materials as described above by ring openingpolyperization by using at least one member selected from citric acid,lactic acid, and ascorbic acid for the catalyst, and an anionicsurfactant for the emulsifier.

The anionic surfactant is preferably the one listed in JapaneseStandards of Quasi-drug Ingredients (JSQI) 2006 and the one notrestricted by The Japanese Standards of Cosmetic Ingredients in thePharmaceutical Affairs Law, and the one which is less irritant, and theone not restricted by poisonous or deleterious substance in thePoisonous and Deleterious Substances Control Act, or Law concerningPollutant Release and Transfer Register (PRTR).

Examples of such anionic surfactants include N-acylamino acid salts,N-acyltaurinates, aliphatic soaps, and alkylphosphate salts, and thepreferred are those which are highly soluble in water and those nothaving polyethylene oxide chain. The anionic surfactant is morepreferably selected from N-acylamino salts, N-acyltaurinates, aliphaticsoaps, and alkylphosphate salts, especially N-acylamino acid salts inwhich the acyl group has 10 to 20 carbon atoms, N-acyltaurinates inwhich the acyl group has 10 to 20 carbon atoms, aliphatic soaps having10 to 20 carbon atoms, and alkylphosphate salts having 10 to 20 carbonatoms. The preferred salt is an alkali metal salt. Sodium lauroylmethyltaurate or sodium myristoyl methyltaurate is most preferred.

Preferably, 0.1 to 20 parts by weight, and more preferably 0.5 to 10parts by weight of the anionic surfactant is used in relation to the 100parts by weight of the cyclic organosiloxane. When the content isexcessively low, the emulsification will not proceed or theemulsification will be extremely unstable, while excessively highcontent may lead to insufficient reaction of the cyclic organosiloxane.

A nonionic surfactant such as polyoxyethylene alkylether may be used incombination with the anionic surfactant. However, use of nonionicsurfactant alone can not retain its surfactant activity under the hightemperature, acidic conditions of the polymerization.

The acid catalyst used for the polymerization catalyst is preferably theone not restricted by The Japanese Standards of Cosmetic Ingredients inthe Pharmaceutical Affairs Law, and the one listed in Japanese Standardsof Quasi-drug Ingredients 2006, and the one not restricted by poisonousor deleterious substance in the Poisonous and Deleterious SubstancesControl Act, or Law concerning Pollutant Release and Transfer Register.Examples include citric acid, lactic acid, and ascorbic acid, and thepreferred is citric acid.

Preferably, 0.01 to 10 parts by weight, and more preferably 0.2 to 2parts by weight of the catalyst is used in relation to 100 parts byweight of the cyclic organosiloxane. Use of an excessively low amountmay result in the insufficient reaction while use of too much catalystresults in the larger amount of the alkali required for neutralization,and this may lead to decrease of the solid content in the system orinstability of the emulsion due to the increase metal ion.

As described above, conventional catalysts such asdodecylbenzenesulfonic acid, hydrochloric acid, and sulfuric acid arenot preferable for use in the present invention. The catalyst used inthe present invention is preferably the one wherein the skin irritancyas described below is up to 10.

In this case, even if the strong acid conventionally used is substitutedwith a weak acid such as acetic acid or butyric acid, unreacted materialmay be left or the resulting product may have a small molecular weight,failing to obtain a product having necessary property.

By using ascorbic acid, citric acid or lactic acid and adjusting thepolymerization temperature, the polymerization time and the amount ofacid, there can be obtained good cosmetic material.

When the emulsion polymerization is conducted by using the ingredientsas described above, the amount of the water is preferably 50 to 200parts by weight in relation to 100 parts by weight of cyclicorganosiloxane.

In the present invention, the polymerization as described above may beconducted by the method and conditions known in the art. When thecatalyst used is a weak acid in the polymerization, higher temperaturetends to result in the higher degree of polymerization. In the presentinvention, the temperature preferably used in the polymerization is 55to 85° C., more preferably 65 to 75° C. The polymerization time isproperly selected although it is preferably about 1 to 40 hours. Too lowpolymerization temperature such as room temperature may not cause thering opening or may insufficiently cause the ring opening. Too highpolymerization temperature may not keep the stability of the emulsion.

In the present invention, the straight chain or branchedorganopolysiloxane is obtained in the form of an emulsion, and theresulting emulsion may be used either without further dilution orconcentration, or with dilution or concentration to a solidconcentration of 20 to 50% by weight, and in particular, 30 to 50% byweight.

The mixing of the reaction product of an amino group-containingorganoxysilane and an acid anhydride (the component (B)) with theorganopolysiloxane (the component (A)) and the drying results in theformation of a cured silicone which has undergone three dimensionalcrosslinking. Preferably, the reaction product is the aminogroup-containing alkoxysilane and the dicarboxylic anhydride, and in thepresent invention, the amino group-containing organoxysilane ispreferably an ethoxy group-containing silane in view of the cosmeticpurpose.

The starting amino group-containing organoxysilane is the onerepresented by the following general formula (2):A(R)_(g)Si(OR)_(3-g)  (2)wherein R is as defined above, A is an amino-containing grouprepresented by the formula —R¹(NHR¹)_(h)NHR² wherein R¹ is independentlya divalent hydrocarbon group such as an alkylene group containing 1 to 6carbon atoms. Examples of R¹ include methylene, ethylene, propylene,butylene, or hexylene group. R² is R or hydrogen atom, and h is aninteger of 0 to 6, preferably 0 or 1, and g is 0, 1, or 2. Examplesinclude:

(C₂H₅O)₃SiC₃H₆NH₂,

(C₂H₅O)₂(CH₃)SiC₃H₆NH₂,

(C₂H₅O)₃SiC₃H₆NHC₂H₄NH₂,

(C₂H₅O)₂(CH₃)SiC₃H₆NHC₂H₄NH₂,

(CH₃O)₃SiC₃H₆NH₂,

(CH₃O)₂(CH₃)SiC₃H₆NH₂,

(CH₃O)₃SiC₃H₆NHC₂H₄NH₂, and

(CH₃O)₂(CH₃)SiC₃H₆NHC₂H₄NH₂.

Since the alcohol generated is preferably ethanol, the OR group is mostpreferably ethoxy group.

The acid anhydride added for reaction with the amino group-containingorganoxysilane is preferably a dicarboxylic anhydride, and the onepreferable for cosmetic purpose is succinic anhydride.

Amount of the acid anhydride reacted is preferably 10 to 60 parts byweight, and more preferably 40 to 60 parts by weight in relation to 100parts by weight of the amino group-containing organoxysilane.Excessively low amount of the acid anhydride may result in low rubberproperty, and excessive amount may result in the yellowing of thereaction product.

The reaction process between the amino group-containing organoxysilaneand the acid anhydride may be readily accomplished at room temperatureor under heated conditions and, if desired, in a hydrophilic organicsolvent depending on the blend ratio of these components. Exemplaryhydrophilic organic solvent used in this reaction include alcohols suchas methanol, ethanol, isopropanol, and butanol, ketones such as acetoneand methyl ethyl ketone, acetonitrile, and tetrahydrofuran. Thehydrophilic organic solvent may be used in an amount of about 0 to 100%by weight of the reaction product.

The reaction temperature is not particularly limited as long as thetemperature is at least room temperature, and the reaction temperatureis preferably 20 to 100° C. The reaction time is not particularlylimited, and the reaction time is preferably 1 to 4 hours.

When the reaction between the amino group-containing organoxysilane andthe acid anhydride is conducted by using a hydrophilic organic solvent,the component (B) may be used either with or without removal of thesolvent.

The solid content (namely, the reaction product between the aminogroup-containing organoxysilane and the acid anhydride) in the reactionproduct is preferably in the range of 10 to 40% by weight and morepreferably about 20 to 30% by weight. Elastomeric property will beinsufficient when the solid content is too low, while excessively highcontent invites instability of the emulsion.

Amount of the reaction product (B) of the amino group-containingorganoxysilane and the acid anhydride is 0.5 to 20 parts by weight, andpreferably 1 to 10 parts by weight in relation to 100 parts by weight ofthe organopolysiloxane (A) containing at least two hydroxyl groupsbonded to the silicon atom per molecule. Excessively low content of thecomponent (B) results in poor rubber property while excessively highcontent results in the unstability of the emulsion and hard texture.

Mixing of the components (A) and (B) by a method known in the art using,for example, a stirrer, propeller agitator, or the like results in theformation of a crosslinkable silicone rubber emulsion emulsified anddispersed in water. The mixing may be conducted for 5 to 30 minutes, andpreferably, at a temperature of 10 to 30° C. As described above, mixingand curing of the component (A) and the component (B) results in theformation of a cured silicone which has undergone the three dimensionalcrosslinking.

The solid content in the silicone rubber emulsion is preferably about 20to 50% by weight, and more preferably 30 to 50% by weight.

The resulting silicone rubber emulsion may preferably have a viscosityas measured by a B viscometer of 10 to 5,000 mPa·s, and more preferably50 to 1,000 mPa·s.

For use of the silicone rubber emulsion in producing a cosmeticpreparation, the intrinsic viscosity as measured by an Ubbelohdeviscometer is preferably 0.1 to 0.9 mm²/s, and more preferably 0.3 to0.9 mm²/s so that the skin does not feel difference in rubber texture.

In this case, the viscosity can be adjusted by the addition ofcarboxyvinyl polymer, polyacrylic acid, or acrylic acid-acrylatecopolymer.

With regard to the average particle diameter measured by a laserdiffraction particle size distribution analyzer, the silicone rubberemulsion may have an average particle diameter of preferably up to 1 μm,and more preferably 100 to 300 nm.

The pH of the silicone rubber emulsion is preferably in the range of 6to 8.

As described above, silicone emulsions have been used in the form ofpowder due to insufficiency in the storage stability, separation, andthe like of the conventional silicone emulsions. In contrast, thesilicone rubber emulsion of the present invention has high storagestability with no separation even after 1 month.

The resulting silicone rubber emulsion is capable of forming a rubberfilm, and this film may be imparted with water repellency, steampermeability, confortability, and the like, and also, with waterresistance by crosslinking. Because of the reduced skin irritancy, thesilicone rubber emulsion is highly expected for use in cosmeticapplications such as hair-care preparations, skin-care preparations,make-up preparations, body-care preparations, sun screen, and inparticular, for skin-care applications.

The crosslinkable silicone rubber emulsion is preferably incorporated ata solid content of 5 to 50% by weight of the entire cosmeticpreparation. Sufficient effect may not be realized when the content isless than 5% by weight, while content in excess of 50% by weight mayresult in excessive rubber property unsuitable for cosmetic application.For example, Example 1 as described below is a mixture of 223 parts byweight (100 parts by weight of solid content) of the emulsion ofPreparation Example 1, 10 parts by weight (5 parts by weight of solidcontent) of the solution of Preparation Example 11, 200 parts by weightof isohexadecane, and 200 parts by weight of KF-6105 (manufactured byShin-Etsu Chemical Co., Ltd. polyglycerin-modified silicone oil).Accordingly, content crosslinkable silicone rubber emulsion is105/633=16.5% by weight.

The cosmetic preparation may also include an oily ingredient, solvent,powder, and the like in addition to the crosslinkable silicone rubberemulsion invention.

Exemplary oily ingredients include hydrocarbons, silicone oils,triglycerides, ester oils, fats, waxes, higher fatty acids, and higheralcohols, and the particularly preferred are low boiling point siliconeoil, low boiling point isoparaffin hydrocarbon, and triglycerides, andester oils.

The content of the oily ingredient in the cosmetic preparation isproperly selected from the type of the cosmetic preparation and is suchan amount that the effect of the cosmetic preparation is not harmed,although the oily ingredient is preferably incorporated in an amount of0.1 to 95% by weight, more preferably 1 to 80% by weight in the cosmeticpreparation. If the amount is less than 0.1% by weight, the effect ofthe oily ingredient such as slippery property and moisture property maynot be exerted. If the amount is more than 95% by weight, the stabilitymay become inferior.

Exemplary solvents include lower to semi-higher alcohols and aromaticalcohols, and use of a lower alcohol such as isopropyl alcohol ispreferable.

The content of the solvent in the cosmetic preparation is properlyselected from the type of the cosmetic preparation and is such an amountthat the effect of the cosmetic preparation, although the solvent ispreferably incorporated in an amount of 0.1 to 80% by weight, morepreferably 1 to 50% by weight in the cosmetic preparation.

The powder is not particularly limited as long as it can be used innormal make up preparation. Exemplary powders include cololants such asan inorganic color pigment, inorganic white pigment, and organicpigment, a pearl agent, an extender pigment, and organic powders. Ifdesired in particular application, a powder having the surface coveredwith an oily ingredient such as silicone may also be used.

The content of the powder is properly selected from the type of thecosmetic preparation and is such an amount that the effect of thecosmetic preparation is not harmed, although the powder is preferablyincorporated in an amount of 0.1 to 95% by weight, more preferably 0.1to 50% by weight, most preferably 0.5 to 40% by weight in the cosmeticpreparation.

The method of incorporating the above ingredients may be properlyselected. For example, the crosslinkable silicone rubber emulsion issimply mixed with the other suitable ingredients homogenously.Alternatively, the other suitable ingredients are preliminarilyemulsified with an emulsifier such as homogenizer, colloid mill or linemixer or preliminarily mixed homogenously, and the crosslinkablesilicone rubber emulsion is added and dispersed therein.

In addition to the components as described above, the cosmeticpreparation of the present invention may further comprise a surfactant,oily ingredient, macromolecular compound, gelation agent, alkalineagent, polyhydric alcohol, pH adjusting agent, UV absorbent,antioxidant, antiseptic, antiphlogistic, skin care component, flavor,and other components commonly incorporated in a cosmetic preparationsuitable for the application of the preparation at a quantitative andqualitative range not adversely affecting the merits of thecrosslinkable silicone rubber emulsion of the present invention.

Exemplary cosmetic preparations of the present invention include make uppreparations such as foundation, white powder, eye shadow, eye liner,eye blow pencil, cheek blusher, lip stick, and nail color; base cosmeticpreparations such as milky lotion, cream, lotion, calamine lotion,sunscreen, sun tan lotion, aftershave lotion, pre-shave lotion, packpreparations, antiacne preparation, and essence; hair cosmeticpreparations such as shampoo, rinse, conditioner, hair color, hairtonic, setting agent, hair restorer agent, and hair permanent agent;body powder, deodorant preparation, depilatory, soap, body shampoo, bathagent, hand soap, and perfume. The crosslinkable silicone rubberemulsion of the present invention is less irritant to the skin, andtherefore, its use for skin-care preparations such as base cosmeticpreparations is preferable.

EXAMPLES

Next, the present invention is described in further detail by referringto Preparation Examples, Examples, and Comparative Examples which by nomeans limit the scope of the present invention. In the followingExamples, “parts” and “%” are respectively “parts by weight” and “% byweight”.

Component (A) Comparative Preparation Example 1

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g oftriethoxyphenylsilane, and 5 g of sodium lauryl sulfate in 45 g of purewater, and a solution of 5 g of dodecylbenzene sulfonic acid in 45 g ofpure water were charged in a 2 L polyethylene beaker, and the mixturewas emulsified by using a homomixer. The emulsion was diluted bygradually adding 400 g of water to the emulsion, and then, passed twicethrough a high pressure homogenizer at a pressure of 300 kgf/cm² tothereby obtain a homogeneous white emulsion. This emulsion wastransferred to a 2 L glass flask equipped with a stirrer, thermometer,and reflux condenser, and allowed to polymerize at 50° C. for 24 hours.After aging at 10° C. for 24 hours, 12 g of 10% aqueous solution ofsodium carbonate was added for neutralization until the pH was 6.2. Thisemulsion had an involatile content after drying at 105° C. for 3 hoursof 45.4%, and the organopolysiloxane in the emulsion was in the state ofan unflowable soft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Comparative PreparationExample 1] was thereby obtained.

Comparative Preparation Example 2

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 5 g of sodium lauryl sulfate in 45 g of purewater, and a solution of 14 g of 35% hydrochloric acid in 36 g of waterwere charged in a 2 L polyethylene beaker, and the mixture wasemulsified by using a homomixer. The emulsion was diluted by graduallyadding 400 g of water to the emulsion, and then, passed twice through ahigh pressure homogenizer at a pressure of 300 kgf/cm² to thereby obtaina homogeneous white emulsion. This emulsion was transferred to a 2 Lglass flask equipped with a stirrer, thermometer, and reflux condenser,and allowed to polymerize at 50° C. for 24 hours. After aging at 10° C.for 24 hours, 12 g of 10% aqueous solution of sodium carbonate was addedfor neutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 44.2%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Comparative PreparationExample 2] was thereby obtained.

Comparative Preparation Example 3

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 5 g of sodium lauryl sulfate in 45 g of purewater, and 2 g of butyric acid were charged in a 2 L polyethylenebeaker, and the mixture was emulsified by using a homomixer. Theemulsion was diluted by gradually adding 400 g of water to the emulsion,and then, passed twice through a high pressure homogenizer at a pressureof 300 kgf/cm² to thereby obtain a homogeneous white emulsion. Thisemulsion was transferred to a 2 L glass flask equipped with a stirrer,thermometer, and reflux condenser, and allowed to polymerize at 50° C.for 24 hours. After aging at 10° C. for 24 hours, 12 g of 10% aqueoussolution of sodium carbonate was added for neutralization until the pHwas 6.2. This emulsion had an involatile content after drying at 105° C.for 3 hours of 41.0%, and the organopolysiloxane in the emulsion was inthe state of an unflowable soft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Comparative PreparationExample 3] was thereby obtained.

Comparative Preparation Example 4

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 5 g of sodium lauryl sulfate in 45 g of purewater, and 2 g of acetic acid were charged in a 2 L polyethylene beaker,and the mixture was emulsified by using a homomixer. The emulsion wasdiluted by gradually adding 400 g of water to the emulsion, and then,passed twice through a high pressure homogenizer at a pressure of 300kgf/cm² to thereby obtain a homogeneous white emulsion. This emulsionwas transferred to a 2 L glass flask equipped with a stirrer,thermometer, and reflux condenser, and allowed to polymerize at 50° C.for 24 hours. After aging at 10° C. for 24 hours, 12 g of 10% aqueoussolution of sodium carbonate was added for neutralization until the pHwas 6.2. This emulsion had an involatile content after drying at 105° C.for 3 hours of 40.8%, and the organopolysiloxane in the emulsion was inthe state of an unflowable soft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Comparative PreparationExample 4] was thereby obtained.

Preparation Example 1

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 5 g of sodium lauroyl methyltaurate in 95 gof pure water, and a solution of 3.8 g of citric acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 42 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 44.8%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Preparation Example 11]was thereby obtained.

Preparation Example 2

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 5 g of sodium lauroyl methyltaurate in 95 gof pure water, and a solution of 1.9 g of citric acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 24 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 44.7%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Preparation Example 2]was thereby obtained.

Preparation Example 3

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 10 g of sodium myristoyl methyltaurate in 90g of pure water, and a solution of 3.8 g of citric acid were charged ina 2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 42 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 44.5%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Preparation Example 3]was thereby obtained.

Preparation Example 4

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 10 g of sodium lauroyl methyltaurate in 90 gof pure water, and a solution of 3.8 g of citric acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 45 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 45.0%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Preparation Example 4]was thereby obtained.

Preparation Example 5

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 5 g of sodium lauroyl methyltaurate in 95 gof pure water, and a solution of 7.6 g of citric acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 60 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 42.7%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Preparation Example 5]was thereby obtained.

Preparation Example 6

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 25 g of sodium lauroyl methyltaurate in 75 gof pure water, and a solution of 3.8 g of citric acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 45 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 45.2%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion [Preparation Example 6]was thereby obtained.

Preparation Example 7

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 10 g of sodium lauroyl methyltaurate in 75 gof pure water, and a solution of 7.6 g of lactic acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 30 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 44.8%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion composition [PreparationExample 7] was thereby obtained.

Preparation Example 8

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofphenyltriethoxysilane, and 10 g of sodium lauroyl methyltaurate in 75 gof pure water, and a solution of 10 g of L-ascorbic acid were charged ina 2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 45 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 44.7%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion composition [PreparationExample 8] was thereby obtained.

Preparation Example 9

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofmethyltriethoxysilane, and 10 g of sodium lauroyl methyltaurate in 75 gof pure water, and a solution of 3.8 g of citric acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 45 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 44.7%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion composition [PreparationExample 9] was thereby obtained.

Preparation Example 10

A solution of 498 g of octamethylcyclotetrasiloxane, 2 g ofmethyltriethoxysilane, and 5 g of sodium lauroyl methyltaurate in 75 gof pure water, and a solution of 3.8 g of citric acid were charged in a2 L polyethylene beaker, and the mixture was emulsified by using ahomomixer. The emulsion was diluted by gradually adding 400 g of waterto the emulsion, and then, passed twice through a high pressurehomogenizer at a pressure of 300 kgf/cm² to thereby obtain a homogeneouswhite emulsion. This emulsion was transferred to a 2 L glass flaskequipped with a stirrer, thermometer, and reflux condenser, and allowedto polymerize at 70° C. for 24 hours. After aging at 10° C. for 24hours, 45 g of 10% aqueous solution of sodium carbonate was added forneutralization until the pH was 6.2. This emulsion had an involatilecontent after drying at 105° C. for 3 hours of 43.2%, and theorganopolysiloxane in the emulsion was in the state of an unflowablesoft gel having an average composition of[(CH₃)₂SiO_(2/2)]/[(C₆H₅)SiO_(3/2)] of 100/0.1 (molar ratio) with itsterminal capped with hydroxy group. An emulsion composition [PreparationExample 10] was thereby obtained.

[Analysis]

The resulting emulsions were evaluated for their evaluation residue,viscosity, average particle diameter, intrinsic viscosity, storagestability by the procedure as described below. The results of theevaporation residue, viscosity, average particle diameter, and intrinsicviscosity are shown in Table 1.

Measurement of Evaporation Residue

About 1 g of the sample was weighed and placed on an aluminum foil dish,and heated in a dryer kept at 105 to 110° C. After heating for 1 hour,the sample was removed from the dryer and allowed to cool in adesiccator. The sample after drying was weighed and the evaporationresidue was calculated by the following equation:

$R = {\frac{T - L}{W - L} \times 100}$

-   R: evaporation residue (%)-   W: weight (g) of the aluminum foil dish and the sample before the    drying-   L: weight (g) of the aluminum foil dish-   T: weight (g) of the aluminum foil dish and the sample after the    drying-   Size of the aluminum foil dish: diameter 70 mm, height 12 mm    Measurement of Viscosity Using B Viscometer

The sample solution was kept at 23±0.5° C., and the viscosity wasmeasured by BM viscometer (No. 1 rotor, 6 rpm).

Measurement of Average Particle Diameter

0.01 g of the sample was weighed and evaluated for average particlediameter (the value of the particle diameter corresponding to 50% of theparticle size cumulative distribution) using a laser diffractionparticle size distribution analyzer (product name, LA-950V2 manufacturedby Horiba) to measure under the circulation flow rate 2 and agitationspeed 2.

Measurement Conditions

Measurement temperature: 25±1° C.

Solvent: ion exchanged water

Measurement of Intrinsic Viscosity

20 g of the emulsion was mixed with 20 g of IPA (isopropylalcohol) tobreak the emulsion to thereby obtain about 4.5 g of the silicone resin.After discarding IPA, the remaining rubbery silicone resin was driedovernight at 60° C., and measured for its viscosity at 25° C. by usingUbbelohde viscometer. Intrinsic viscosity was calculated from themeasurement time (specific viscosity of the toluene is 0.65, and theintrinsic viscosity is calculated from this value). See the followingequation.

-   (1) toluene solution of dimethylpolysiloxane at a concentration of 1    g/100 mL was prepared to determine the specific viscosity ηsp at 25°    C.    ηsp=(η/η0)−1    -   η0: viscosity of toluene, η: viscosity of the solution-   (2) Next, ηsp is substituted in the relational equation of Huggins    to calculate intrinsic viscosity [η].    ηsp=[η]+K′[η] ²    -   K′: Huggins constant K′=0.3        -   (applicable when [η]=1 to 3)

REFERENCE

-   Nakamuta, Journal of the Chemical Society of Japan, 77 858 [1956]

The intrinsic viscosity is preferably in the range of 0.3 to 0.9 mm²/s.

Storage Stability

Storage stability after storing at room temperature for 1 month wasconfirmed. Change in viscosity and particle diameter was also confirmed.Separation or other changes were not found in all of PreparationExamples, and no change was also found for the viscosity and theparticle size. Sufficient long term stability was thereby confirmed.

TABLE 1 Comparative Preparation Example Preparation Example 1 2 3 4 1 23 4 5 6 7 8 9 10 Evaporation 45.1 44.2 41.0 40.8 44.8 44.7 44.5 45.042.7 45.2 44.8 44.7 44.7 43.2 residue (%) Viscosity 100 100 20 30 30 130100 100 50 200 100 150 150 100 (mPa · s) Average 200 200 200 200 300 300200 200 200 150 200 200 200 200 particle diameter (nm) Intrinsic 0.820.85 0.34 0.30 0.75 0.36 0.48 0.78 0.77 0.68 0.32 0.28 0.72 0.38viscosity (mm³/s)

Component (B) Preparation Example 11

154 g of succinic anhydride was dissolved in 500 g ethanol, and 346 g of3-aminopropyltriethoxysilane was added to the solution at roomtemperature for 1 hour, and the reaction was allowed to proceed at 80°C. for 24 hours by refluxing the ethanol to obtain a pale yellowtransparent solution [B-1] containing 50% of the component (B). Thissolution had an involatile content after drying at 105° C. for 3 hoursof 45.1%. In the instrumental analysis of IR, GC, NMR, GCMS, and thelike, about 60% was mixture of those represented by the followingformulae and the remaining about 40% was oligomers derived therefrom.(C₂H₅O)₃SiC₃H₆—NHCO—CH₂CH₂COOH(C₂H₅O)₃SiC₃H₆—NH₃ ⁺⁻OCOCH₂CH₂COOC₂H₅

Preparation Example 12

190 g of succinic anhydride was dissolved in 550 g ethanol, and 346 g of3-aminopropyltriethoxysilane was added to the solution at roomtemperature for 1 hour, and the reaction was allowed to proceed at 80°C. for 24 hours by refluxing the ethanol to obtain a pale yellowtransparent solution [B-2] containing 50% of the component (B). Thissolution had an involatile content after drying at 105° C. for 3 hoursof 44.1%. In the instrumental analysis of IR, GC, NMR, GCMS, and thelike, about 60% was mixture of those represented by the followingformulae and the remaining about 40% was oligomers derived therefrom.(C₂H₅O)₃SiC₃H₆—NHCO—CH₂CH₂COOH(C₂H₅O)₃SiC₃H₆—NH⁺⁻OCOCH₂CH₂COOC₂H₅

Comparative Example 1

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 222 parts (solid content, 100 parts) of theemulsion obtained in Comparative Preparation Example 1. After stirringthe mixture at room temperature for about 10 minutes with a stirrer, themixture was filtered by a 80 mesh filter, and 200 parts of isohexadecaneand 200 parts of KF-6105 manufactured by Shin-Etsu Chemical Co., Ltd.were added to the filtrate. The mixture was agitated at room temperaturefor 10 minutes with an agitator to thereby obtain an O/W/O emulsioncream [Comparative Example 1].

Comparative Example 2

40 parts (solid content, 20 parts) of the solution of the PreparationExample 11 was mixed with 222 parts (solid content, 100 parts) of theemulsion obtained in Comparative Preparation Example 1, and theprocedure of Comparative Example 1 was repeated to thereby obtain anO/W/O emulsion cream [Comparative Example 2].

Comparative Example 3

200 parts of isohexadecane and 200 parts of KF-6105 manufactured byShin-Etsu Chemical Co., Ltd. were mixed with 167 parts of KM-903manufactured by Shin-Etsu Chemical Co., Ltd. (solid content, 100 parts).The mixture was agitated with an agitator to obtain an O/W/O emulsioncream [Comparative Example 3].

Comparative Example 4

200 parts of isohexadecane and 200 parts of KF-6105 manufactured byShin-Etsu Chemical Co., Ltd. were mixed with 167 parts of KM-910manufactured by Shin-Etsu Chemical Co., Ltd. (solid content, 100 parts).The mixture was agitated with an agitator to obtain an O/W/O emulsioncream [Comparative Example 4].

Comparative Example 5

200 parts of isohexadecane and 200 parts of KF-6105 manufactured byShin-Etsu Chemical Co., Ltd. were mixed with 226 parts of the emulsionobtained in Comparative Preparation Example 2. The mixture was agitatedwith an agitator to obtain an O/W/O emulsion cream [Comparative Example5].

Comparative Example 6

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 224 parts (solid content, 100 parts) of theemulsion obtained in Comparative Preparation Example 3, and theprocedure of Comparative Example 1 was repeated to thereby obtain anO/W/O emulsion cream [Comparative Example 6].

Comparative Example 7

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 245 parts (solid content, 100 parts) of theemulsion obtained in Comparative Preparation Example 4, and theprocedure of Comparative Example 1 was repeated to thereby obtain anO/W/O emulsion cream [Comparative Example 7].

Example 1

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 223 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 1, and the procedure ofComparative Example 1 was repeated for emulsification and dispersion inwater to thereby obtain an O/W/O emulsion cream [Example 1].

Example 2

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 224 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 2, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 2].

Example 3

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 225 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 3, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 3].

Example 4

10 parts (solid content, 20 parts) of the solution of the PreparationExample 11 was mixed with 223 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 1, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 4].

Example 5

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 222 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 4, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 5].

Example 6

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 234 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 5, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 6].

Example 7

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 221 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 6, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 7].

Example 8

10 parts (solid content, 5 parts) of the solution of the PreparationExample 12 was mixed with 223 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 1, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 8].

Example 9

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 223 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 7, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 9].

Example 10

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 224 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 8, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 10].

Example 11

10 parts (solid content, 5 parts) of the solution of the PreparationExample 11 was mixed with 231 parts (solid content, 100 parts) of theemulsion obtained in Preparation Example 9, and the procedure ofComparative Example 1 was repeated to thereby obtain an O/W/O emulsioncream [Example 11].

[Evaluation Method]

The thus obtained O/W/O emulsion creams were evaluated for theirevaporation residue, texture (spreadability), softness, tackiness, skinirritancy by the procedure as described below. The results are shown inTable 2.

Evaporation Residue

The evaporation residue was measured as in the case of the emulsion asdescribed above.

Texture (Spreadability)

The spreadability was evaluated by placing 0.5 g of the cream on anartificial leather, and spreading the cream by moving one fingertip incircles (n=20). The spreadability of the Comparative Example 4 preparedby using a commercially available product was evaluated B, and theevaluation was conducted by using the Comparative Example 4 for thestandard.

A: spreadability higher than Comparative Example 4

B: equivalent with Comparative Example 4

C: spreadability lower than Comparative Example 4

Softness

The Softness of the Comparative Example 4 prepared by using acommercially available product was evaluated B, and the evaluation wasconducted by using the Comparative Example 4 for the standard.

A: lighter and softer texture than Comparative Example 4

B: equivalent with Comparative Example 4

C: inferior to Comparative Example 4

The evaluation was conducted by 10 people. The evaluation result of 6 ormore people is shown in the table.

Tackiness

The tackiness of the Comparative Example 4 prepared by using acommercially available product was evaluated B, and the evaluation wasconducted by using the Comparative Example 4 for the standard.

-   -   A: less oily and tacky than Comparative Example 4. Smooth with        no tackiness.    -   B: equivalent with Comparative Example 4    -   C: inferior to Comparative Example 4

The evaluation was conducted by 10 people. The evaluation result of 6 ormore people is shown in the table.

Skin Irritancy Test

Skin irritancy was evaluated by patch test (closed patch test) commonlyused in confirming skin irritancy of cosmetic preparations.

A circular filter paper having a diameter of about 5 mm with the O/W/Oemulsion cream, and this paper was adhered to upper arm by using analuminum disk (Finn chamber) having the same diameter as the filterpaper so that the filter paper was covered by the Finn chamber. The Finnchamber was secured by using a tape.

After 48 hours, the filter tape was peeled off the skin (patch removal),and the skin irritancy was evaluated by the skin reaction after 1 hourand 24 hours.

<Criteria>

-   -   No reaction: −    -   Slight erythema: ±    -   Erythema: +    -   Erythema and edema: ++    -   Erythema, edema, and small blisters: +++

The point given for each criterion was −:0, ±:0.5, +:1.0, ++:2.0, and+++:3.0. The point multiplied by the number of people showing thecorresponding reaction was used as the score. The score of 1 hour afterthe patch removal (49 hour evaluation) and 24 hours after the patchremoval (72 hour evaluation) were calculated. The score divided by thenumber of subjects and multiplied by 100 is irritancy index. Theproducts with the irritancy index of up to 10 are safe products, 11 to30 are acceptable products, and improvement is required for the productswith the index in excess of 30.

Detailed results of the skin irritancy test are shown in Table 3.

Confirmation of Crosslinkability

Crosslinkability was confirmed by the actual progress of thecrosslinking. 5 g of the emulsion was dried at 105° C. for 3 hours toobtain a rubbery oil. 1 g of this oil component was dissolved in 100 gof toluene, and after stirring the solution for 1 hour and filtration,the insoluble content was collected by filtration through a nylon filtercloth and dried at 105° C. for 1 hour. The more residue after the dryingmeans higher degree of crosslinking. The value of 0.05% or higher wasdetermined to indicate the crosslinking.Increase in the filter cloth weight (g)/1 g=%  equation:

TABLE 2 Content Comparative Example Example (parts by weight) 1 2 3 4 56 7 1 2 3 4 5 6 7 8 9 10 11 (A) Com- 1 100 100 (Solid parative 2 100con- Prep- 3 100 tent) aration Example 4 100 Prep- 1 100 100 100 aration2 100 Example 3 100 4 100 5 100 6 100 7 100 8 100 9 100 (B) Prep- 11 520 5 5 5 5 5 20 5 5 5 5 5 5 (Solid aration 12 5 con- Example tent)KM-903 100 (solid content) KM-910 100 (solid content) Confirmation ofthe 0.10 0.19 0.02 0.02 0.01 0.01 0.02 0.12 0.09 0.12 0.25 0.10 0.200.14 0.15 0.15 0.13 0.19 crosslinkability (%) Isohexadecane 200 200 200200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 KF-6105 200200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 Re-Evaporation 48 48 53 53 48 47 47 47 48 48 48 47 48 48 48 48 48 48 sultsresidue (%) of Texture B B B B B B B A A A A B B B B B B B eval-(spread- uation ability) Softness A A B B B B B A A A A A A A A A A ATackiness A A B B B B B A A A A A A A A A A A Irritancy 15 12.5 0 0 17.55 12.5 0 2.5 2.5 0 2.5 5 2.5 2.5 0 0 2.5 index (after 49 hours)Irritancy 5 0 0 0 7.5 0 0 0 0 0 0 0 0 0 0 0 0 0 index (after 72 hours)KM-903: nonionic emulsion prepared by using a highly polymerizeddimethicone diluted with a dimethicone having medium viscosity for thebase oil (solid content, 60%) manufactured by Shin-Etsu Chemical Co.,Ltd. KM-910: nonionic emulsion prepared by using a highly polymerizeddimethicone having a degree of polymerization higher than KM-903 dilutedwith a dimethicone having medium viscosity for the base oil (solidcontent, 60%) manufactured by Shin-Etsu Chemical Co., Ltd. KF-6105: apolyglycerin-modified silicone oil manufactured by Shin-Etsu ChemicalCo., Ltd.

As demonstrated by the results shown in Table 2, Comparative Examples 3and 4 prepared by using KM-903 and KM-910 can not be regarded aqueous,and emulsification and dispersion of the silicone oil was required. Thisis commercially disadvantageous for the production of the silicone resinemulsion which is used as the main ingredient of a cosmetic preparation.

In contrast, the Examples using the silicone rubber emulsion of thepresent invention had the texture (spreadability) comparable to theO/W/O emulsion cream of Comparative Example 1. With regard to thesoftness, the Examples using the silicone rubber emulsion of the presentinvention had characteristic rubber elasticity compared to simpledimethicone gum, and therefore, they have light and soft texture.Tackiness is also greatly improved compared to the silicone oil, and thesilicone rubber emulsions of the present invention are advantageous forcosmetic purpose compared to Comparative Examples 3 and 4 also in viewof the tackiness.

Accordingly, performance comparable to those of conventional products isrealized by the use of the silicone rubber emulsions of the presentinvention in producing the cosmetic products. Use of the silicone rubberemulsions of the present invention is also expected to bring the meritsof rubber performance to the cosmetic products.

TABLE 3 Evaluation Evaluation − ± + ++ +++ Irritancy time Point 0 0.51.0 2.0 3.0 Score index Evaluation Comparative 1 49 h No. of subjects 154 1 0 0 3 15 Acceptable Example Score 0 2 1 0 0 product 72 h No. ofsubjects 18 2 0 0 0 1 5 Score 0 1 0 0 0 2 49 h No. of subjects 15 5 0 00 2.5 12.5 Acceptable Score 0 2.5 0 0 0 product 72 h No. of subjects 200 0 0 0 0 0 Score 0 0 0 0 0 3 49 h No. of subjects 20 0 0 0 0 0 0 SafeScore 0 0 0 0 0 product 72 h No. of subjects 20 0 0 0 0 0 0 Score 0 0 00 0 4 49 h No. of subjects 20 0 0 0 0 0 0 Safe Score 0 0 0 0 0 product72 h No. of subjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 5 49 h No. ofsubjects 13 7 0 0 0 3.5 17.5 Acceptable Score 0 3.5 0 0 0 product 72 hNo. of subjects 15 3 0 0 0 1.5 7.5 Score 0 1.5 0 0 0 6 49 h No. ofsubjects 18 2 0 0 0 1 5 Safe Score 0 1 0 0 0 product 72 h No. ofsubjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 7 49 h No. of subjects 15 5 0 00 2.5 12.5 Acceptable Score 0 2.5 0 0 0 product 72 h No. of subjects 200 0 0 0 0 0 Score 0 0 0 0 0 Example 1 49 h No. of subjects 20 0 0 0 0 00 Safe Score 0 0 0 0 0 product 72 h No. of subjects 20 0 0 0 0 0 0 Score0 0 0 0 0 2 49 h No. of subjects 19 1 0 0 0 0.5 2.5 Safe Score 0 0.5 0 00 product 72 h No. of subjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 3 49 h No.of subjects 19 1 0 0 0 0.5 2.5 Safe Score 0 0.5 0 0 0 product 72 h No.of subjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 4 49 h No. of subjects 20 0 00 0 0 0 Safe Score 0 0 0 0 0 product 72 h No. of subjects 20 0 0 0 0 0 0Score 0 0 0 0 0 5 49 h No. of subjects 19 1 0 0 0 0.5 2.5 Safe Score 00.5 0 0 0 product 72 h No. of subjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 649 h No. of subjects 18 2 0 0 0 1 5 Safe Score 0 1 0 0 0 product 72 hNo. of subjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 7 49 h No. of subjects 191 0 0 0 0.5 2.5 Safe Score 0 0.5 0 0 0 product 72 h No. of subjects 20 00 0 0 0 0 Score 0 0 0 0 0 8 49 h No. of subjects 19 1 0 0 0 0.5 2.5 SafeScore 0 0.5 0 0 0 product 72 h No. of subjects 20 0 0 0 0 0 0 Score 0 00 0 0 9 49 h No. of subjects 20 0 0 0 0 0 0 Safe Score 0 0 0 0 0 product72 h No. of subjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 10 49 h No. ofsubjects 20 0 0 0 0 0 0 Safe Score 0 0 0 0 0 product 72 h No. ofsubjects 20 0 0 0 0 0 0 Score 0 0 0 0 0 11 49 h No. of subjects 19 1 0 00 0.5 2.5 Safe Score 0 0.5 0 0 0 product 72 h No. of subjects 20 0 0 0 00 0 Score 0 0 0 0 0

As shown in Table 3, after 49 hours, Comparative Examples 1, 2, and 5were at the level of the acceptable product with some irritancy and notthe level of the safe product. In contrast, no reaction was observed inmost people in the case of Examples 1 to 11, and this demonstratesdramatically reduced irritancy compared to Comparative Examples.

Japanese Patent Application No. 2012-043952 is incorporated herein byreference.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

The invention claimed is:
 1. A method for producing a hair-care preparation, skin-care preparation, make-up preparation, body-care preparation, or sun screen, said method comprising the steps of: producing a crosslinkable silicone rubber emulsion comprising a straight chain or branched organopolysiloxane (A) containing at least two hydroxyl groups bonded to silicon atoms per molecule prepared by ring-opening polymerization, at a temperature of 55 to 85° C., of a cyclic organosiloxane in the presence of an alkoxysilane or its partial hydrolytic condensate or an α,ω-dihydroxy or dialkoxy siloxane oligomer, and in the presence of 50 to 200 parts by weight of water per 100 parts by weight of said cyclic organosiloxane, by using citric acid and/or ascorbic acid as a catalyst in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the cyclic organosiloxane and using an anionic surfactant as an emulsifier, wherein the anionic surfactant is at least one member selected from N-acylamino acid salt, N-acyltaurinate, and aliphatic soap; producing a reaction product (B) of an amino group-containing organoxysilane and an acid anhydride; combining reaction product component (B) and crosslinkable silicone rubber emulsion (A) at a mixing ratio of 0.5 to 20 parts by weight of the component (B) in relation to 100 parts by weight of the organopolysiloxane in the crosslinkable silicone rubber emulsion (A); mixing an oily ingredient and a surfactant with crosslinkable silicone rubber emulsion (A) and reaction product (B) to form a mixture in which the crosslinkable silicone rubber emulsion (A) is present at a solids content of 5 to 50% by weight of said mixture; and stirring said mixture to form said hair-care preparation, skin-care preparation, make-up preparation, body-care preparation, or sun screen in the form of an O/W/O emulsion.
 2. The method according to claim 1 wherein the temperature of the ring-opening polymerization is 65 to 75° C.
 3. The method according to claim 1 wherein the straight chain or branched organopolysiloxane of component (A) is represented by the following general formula (1):

wherein R is independently an alkyl group containing 1 to 20 carbon atoms or an aryl group containing 6 to 20 carbon atoms; X is independently an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, or hydroxyl group; Y is independently X or a group represented by —[O—Si(X)₂]_(c)—X, at least 2 of X and Y being hydroxyl group; letter a is an integer of 0 to 1,000; letter b is an integer of 100 to 10,000; and letter c is an integer of 1 to 1,000; with the proviso that each constitutional repeating unit may be randomly bonded.
 4. The method according to claim 1 wherein the amino group-containing organoxysilane of component (B) is the one represented by the following general formula (2): A(R)_(g)Si(OR)_(3-g)  (2) wherein R is independently an alkyl group containing 1 to 20 carbon atoms or an aryl group containing 6 to 20 carbon atoms, A is an amino-containing group represented by the formula: —R₂(NHR¹)_(n)NHR² wherein R¹ is independently a divalent hydrocarbon group containing 1 to 6 carbon atoms, R² is R or hydrogen atom, and letter h is an integer of 0 to 6, and letter g is 0, 1, or 2, and the acid anhydride is a dicarboxylic acid anhydride.
 5. The method according to claim 1 wherein the catalyst for obtaining the component (A) is citric acid.
 6. The method according to claim 1 wherein the anionic surfactant is used in an amount of 0.1 to 20 parts by weight in relation to 100 parts by weight of the cyclic organosiloxane.
 7. The method of claim 1, wherein said crosslinkable silicon rubber emulsion (A), said reaction product (B), and said oily ingredient are mixed together in a single step.
 8. The method of claim 1, wherein said reaction product (B) and said oily ingredient are mixed with one another in a first step and then said crosslinkable silicon rubber emulsion (A) is added to the resulting mixture and dispersed therein in a second step.
 9. The method of claim 1, wherein said oily ingredient is at least one member selected from the group consisting of hydrocarbons, silicone oils, triglycerides, ester oils, fats, waxes, higher fatty acids, and higher alcohols. 